DE3300579C2 - Anti-parasitic collar for animals and process for its preparation - Google Patents

Description

The invention relates to improvements of antiparasitic Collars for animals. It has been around for some time now Used devices that are suitable, gradually to release a contact insecticide that is used to protect Animals against parasites and especially against ectoparasi are determined. The majority of these devices consists of an insecticide that turns into a matrix Plastic material is included. The slow free of the ectoparasitic product (which is about his Steam or the deposit on the fur of the animal gene) allows effective protection during meh months against parasites.

These various antiparasitic devices that the subject of numerous patents (in particular Applicants' FR-PS 2 447 679, 2 269 859, 2 307 466, 2436 563, 2370 572, 2 213 014, 2 374 853, 2 386 253, 2 386 254, 2 392 606) consist essentially of three Basic elements:

• the insecticide (or the insecticide mixture),
• - The carrier (generally based on a thermo plastic resin),
• - The additives (such as plasticizers, Diffusionsregulato ren, etc.).

The choice of each of the three basic components is very important tig. It is indeed very important to have one against Parasitic effective device to have a long same and regular diffusion possible and completely un harmful to the animal and its environment and in particular This is for young animals.

Although it could handle the majority of the disadvantages of this anti parasitic collars are cleared out and difficult All kinds of problems were overcome, however remains a very significant disadvantage. The animal shows  rapidly or after a certain period of use allergic Appearances that show up in local irritations: Redness of the skin, eczema, dulling of the coat, loss the smoothness of the skin, etc., and / or through all common disorders: vomiting, weight loss, etc.

DE-OS 30 39 881 relates to new ektoparasitizidhaltige Collars for pets made of polyurethane, the spreading agent and ectoparasiticides.

DE-OS 26 58 725 relates to a means of fighting tie rischer Ektoparasiten, which is characterized in that it contains as component a pressure-sensitive adhesive. It contains this agent, for example, the ectoparasiticides or Re active agent in a concentration of 1 to 50% by weight, the pressure-sensitive adhesive in a concentration of 1 to 50 wt .-%, other auxiliaries, such as plasticizers or surfactants in a concentration of 0 to 10 Wt .-% and a solvent in a concentration of 40 to 98% by weight.

DE-OS 24 14 479 relates to an animal collar for fighting of ticks and fleas, characterized in that it consists essentially of a solid vinyl resin, O- (2-isoprop oxyphenyl) -N-methylcarbamate and a plasticizer. The plasticizer may be, for example, an oleic acid ester and in an amount of 20 to 45%.

The aim of the invention is therefore the provision of Collars ectoparasitizider nature, the meet the requirements of the practice better than the previously known devices for the same purpose, in particular skin disorders of the animal completely suppressed while maintaining a strong effectiveness during maintained over a long period of time.

The subject of the invention is an antiparasitic collar for animals of at least one insecticidal substance, one macromolecular carrier and additives characterized thereby is that it is drawing

• (a) at least one free or esterified unsat essential fatty acid with C₁₈ to C₂₂ in association with the insecticidal substance as the active ingredient,
• (b) a thermoplastic solid macromolecular Carriers, except polyurethane,
• (c) additives such as plasticizer and / or inert filler substances and / or dyes and / or deodorants and / or Stabilizers and / or diffusion regulators

that contains therein the proportion of the insecticidal substance between 5 and 25%, the proportion of unsaturated fatty acids between 1 and 10%, the proportion of the macromolecular carrier between 10 and 50% and the proportion of supplements between and 15%, and that it is in the form of two laterally belt connected to form a mixed Doppelrie mens, wherein a belt is the insecticidal substance, the others containing the fatty acid and each of the two parts of the belt Carrier and for the insecticidal substance and for the chosen unsaturated essential fatty acid suitable additives ent holds.

In the context of the present invention it has been found that in the long term the intolerance for insecticidal collars caused by the lack of certain fatty acids, which are necessary for the epithelial system of the animal.

According to the invention, the antiparasitic collar exists among other things from the following two building blocks: a macro molecular solid thermoplastic carrier, except polyurethane, Additives (plasticizers or plasticizers and / or inert fillers, and / or coloring materials and / or deodorants and / or stabilizers and / or the Diffusion controlling agents or diffusion regulators).

According to an advantageous embodiment of the invention the insecticidal substance is selected from the organo Chlorine compounds and / or organophosphorus compounds and / or carbamates and / or pyrethrin, pyrethrum or  Pyrethrinoid compounds and / or formamidines.

According to a specific embodiment of this embodiment, the organochlorine compounds are selected from the group of:
2,2-dichlorovinyldimethyl phosphate (DDVP)
1,2-dibromo-2,2-dichloroethylmethyl phosphate (NALED®),
2-Chloro- (2,4,5-trichlorophenyl) -vinyldimethylphosphate (STIRIFOS®).

According to another specific embodiment, the Organophosphorus compound selected from the group of O, O'-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidinyl) thionophosphate (DIMPYLATE® and O, O-diethyl-O-2-isopro pyl-4-methyl-6-pyrimidinyl) phosphate (DIAZOXON®).

According to another specific embodiment the carbamates selected from 2,2-dimethyl-1,3-benzo dioxol-4-ol (N-methylcarbamate) (BENDIOCARD®), 2-isoprop oxyphenyl (N-methylcarbamate) PROPOXUR®) and 1-naphthyl N-methylcarbamate (CARBARYL®).

According to another specific embodiment the substances of pyrethrin type selected from α-cyano 3-phenoxybenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclo propanecarboxylate (CYPERMETHRIN®), α-cyano-3-phenoxybenzyl 2- (4-chlorophenyl) -3-methyl butyrate (FENVALERATE®), 5-Ben benzyl-3-furylmethyl 2,2-dimethyl-3- (2-oxo-2,3,4,5-tetra hydro-3-thienylidenemethyl) cyclopropanecarboxylate (KADE THRIN®), 3-phenoxybenzyl-2,2-dimethyl-3- (2,2-dichlorovinyl) - cyclopropanecarboxylate (PERMETHRINE®) and (3,4,5,6-tetra hydrophthalimidomethyl) chrysanthemate (NEOPYNAMIN®).

According to another specific embodiment the formamidines selected from N '- (4-chloro-O-tolyl) -N, N- dimethylformamidine (CHLORDIMEFORM®) and N-methyl-N'-2,4- xylyl-N- (N-2,4-xylylformamidoyl) -formamidine (AMITRAZ®).  

According to the invention, the free or esterified unsaturated essential fatty acids selected from Group of oleic acid, linoleic acid, linolenic acid, arachidon acid, 11,14-eicosadienoic acid, docosahexanoic acid and their linear or branched C₁-C₄ esters.

According to another particularly advantageous embodiment form is used as fatty acids the vitamin F.

As a macromolecular solid thermoplastic carrier For example, you can use polyethylene, polpropy len, copolymers of ethylene and propylene, polyacrylates, Vinyl polymers, polyvinyl halides, polyvinyl acetals, Polyvinylidene type compounds and poly aldehydes and preferably the homopolymers of Polyvinyl chlorides and their copolymers with other poly mers.

As plasticizer or plasticizer necessary are, for suppleness, mechanical resistance and the desired surface properties ver For example, you can borrow phosphoric acid esters, such as tricresyl phosphate, phthalic acid esters, such as methyl phthalate, butyl phthalate, octyl phthalate, 2-ethylhexyl phthalate and the esters of adipic acid, azelaic acid, Sebacic acid and maleic acid.

The most commonly added additives are dyes or pigments, deodorizing materials such as Ethylvanil lin, vanillin and linones, stabilizers, lubricants tel, metal complexes (for example of cadmium, barium and zinc); diffusion controlling agents that reduce the porosity Modify the plastic belt by evaporation or Decomposition, starting with the production, such as example, the nitrogen-containing derivatives (benzenesulfonyl hydrazine and trihydrazinotriazine) and the azo derivatives (Azodiisobutyronitrile, Diazoaminobenzene and Azodicarbon amide).  

As fillers that are necessary to the plastic reduce the amount and handling of thermoplasti To facilitate the belt, you can use talc and silicon use dioxide.

According to the invention, the composition of antiparas sitarian collar 5 to 25% insecticidal substance, 1 up to 10% unsaturated essential fatty acid, 10 to 50% macromolecular carrier and 1 to 15% of various Zu sentences.

According to a particularly advantageous embodiment of the Invention is the insecticides associated with the fatty acid Zide substance DIMPYLATE®, associated with vitamin F.

Extensive research has shown that that in certain cases the physicochemical nature the active substances, in particular the physical solid or liquid aspect, the melting point, the boiling point point, the vapor pressure and the thermal or chemical Stability no regular and equal diffusion allowed the two substances simultaneously.

The diffusion rate could in certain Fäl even in substantial proportions. In determined In these cases, it became essential to chemical properties of active substances (of the insect tizids and the fatty acid) to consider before one suitable macromolecular carrier, plasticizer, additives, Fillers and suitable diffusion regulators chosen could be to make a compromise and free Settling velocities of the two active substances to achieve something as similar as possible if not in the are essentially identical.

One of the objects of the invention is the provision an antiparasitic collar suitable for overcome the disadvantages that in certain cases in  incompatibility between an active substance and of an unsaturated essential fatty acid could.

The realization of the two belts made of plastic materials in the invention Collar, each containing one of the active substances with the straps attached to one another laterally, has made it possible to meet the requirements of diffusion and the maximum release.

According to a particularly advantageous embodiment of the Invention, the mixed belt is obtained by Koextru sion or joint extrusion in the heat.

According to another embodiment of the invention receives the mixed belt by molding or pressing. However, it is independent of the manufacturing technique the belt (coextrusion or molding) very simply the Nature of the excipients and the carrier to the physically chemical properties of each of the two active substances to adjust the working conditions.

It follows that while retaining the beschrie compatibility quality the effectiveness of the  antiparasitic device is greatly improved and the Inconvenience in the production and thus the Her maximum costs are reduced.

Among the different techniques used to manufacture the collars according to the invention are suitable is as coextrusion in the heat or hot extrusion designated technique from the industrial point of view the most suitable method.

This latter process, used in the rubber and Plastic industry currently used widely is, leads to the production by coextrusion of a mixed belt starting from a separate extru tion of the two different mixtures by a single ge extrusion or nozzle.

By producing the two different mixtures, each in their composition for the nature of active substance are suitable, one arrives at a more effective final device. This manufacturing wise is particularly favorable if the two active sub punching in their physicochemical properties are very different.

So are the unsaturated essential fatty acids C₁₈-C₂₂ or their ester derivatives in the form of viscous Liquids before, and the invention used insecticidal substances can be liquid compositions (organochlorine compounds, organophosphorus compounds, Pyrethrinoids) or solids (carbamates, formamidines) his.

In addition, each connection group is also through different boiling points or melting points, by Vapor pressures that are very different, as well as through different thermal or chemical stability criteria.  

The skilled person is aware that the nature of makromoleku laren carrier, the nature of plasticizers, the nature of Additives considerably increase the diffusion rate and so that the release and finally the measured Akti influence the quality.

It follows that the association of a carbamate and / or a formamidine with a fatty acid ester not leads to optimal results, as when the together of any part is different.

The result is considered optimal when the diffu sion rates of each of the compounds are similar are.

It is therefore necessary for each substance type used, to adjust the nature of the additives and / or the carrier in such a way sen, that the release of one of the compounds, related to the other as a comparison, accelerated or slowed down becomes velvet.

In appearance, the new collars show the shape a mixed belt, the dimensions of each partly due to the different elements are, like the percentage of active material, the insek ticidal effect and / or protective action of the substance; in the In general, they must meet the condition, one To form belt, which as antiparasitic collar for Pets (dogs or cats) is usable.

In general, the dimensions of the final Belt at about 15 to 30 mm wide and about 2 to 5 mm Thickness, the length being calculated to be around the Neck of the thickest animals can be attached.

It can be seen that collars that are in the dim for each animal type, cat, puppy, dog, big dog, are suitable, are preferred.  

Due to the different percentages, that is, 5 to 25% for the insecticidal substance and 1 to 10% for the fatty acids, the widths are below for each part different.

In general, the widths are 10 to 20 mm for the insecticidal part and at 5 to 10 mm for the fat acid part.

The separate preparation of each of the two mixtures he allows the incorporation of dyes or coloring Substances, pigments, light-reflecting substances or luminescent substances of different nature in every part.

Except for the above collars, the invention includes also other collars, from the following descrip are evident.

The invention includes in particular antiparasitic neck straps for animals according to the protruding neck Bands, as well as suitable means for Her position of these collars.

The following examples serve for further explanation the invention. They concern the realization of he inventive devices, the compositions for the devices, as well as a report on clinical Studies performed on animals.

It is understood that the following examples as well as the clinical report should be used for explanation only without being restrictive.  

Examples of compositions

example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example of the production of a collar

The substances of Example 2 are used.

In a suitable container is intimately mixed 36 kg DIMPYLATE®, 12 kg of neutral vitamin F, 46 kg of isooctyl adipate, 6 kg of epoxidized soybean oil and stains the solution  with red iron oxide (about 1 kg).

In a heating mixer brings 47 kg homopolymer of PVC, 4 kg calcium stearate, 4 kg micro-shredded sili and 4 kg of azodicarbonamide.

With stirring, the above solution is poured into the before standing mixer. The resulting paste is mixed until to achieve a uniform red color. You bring that Mixture to a temperature of about 70 ° C and mixed 30 minutes. The powder thus obtained is in the Beschic kung funnel a Schraubenextrusionsvorrichtung a brought. The extrusion parameters, that is, the Tempe the nozzle, the pressure of the nozzle, the extrusion speed and the cooling temperature are adjusted in such a way that you are equal in appearance and dimensions moderate belt receives.

Then the belt is cut in length and a closure system is clamped to one of the ends.

The obtained insecticidal collar is placed in bag three thick thickness (PVC-aluminum paper) introduced and ver welded.

This manufacturing option is for all examples possible, with modifications due to the physical Nature of the ingredients are carried out.

Example of the production of a mixed double belt

Two mixtures are prepared: Mixture A contains the insecticidal substance and mixture B contains the fat acid.

These two mixtures (of which certain compositions differences will be described below)  after homogenizing, separate into the two Feed hopper of a double-system extruder brought. At the exit, the two go through in the Ab Measurements pre-measure belts a common strand pressing head, inside which the lateral welding he follows.

This stage of manufacture can also be used be carried out by two different extruders, the ver at the output by a single extrusion are bound, which is a lateral attachment of the two original straps together as well as their final ones Dimensioning on the format of the single belt allows.

This system has the advantage of being independent the extrusion parameters such as the temperature of the nozzle, the Pressure and the extrusion speed can regulate.

Example of the composition Example 8

Mixture A

Mixture B

Mixture A

Into a first vessel is intimately mixed 32 kg 95% DIMPYLATE®, 6 kg epoxidized soybean oil, 40 kg 2-ethylhexyl Phthalate and colors the solution by mixing the both iron oxides.

In a heating mixer leads 50 kg of homopolymer of PVC and 4 kg of azodicarbonamide.

Then bring the above with stirring Solution in the mixer, heated for 30 minutes at 70 ° C. and completed by the remaining amount of Homopolymers of PVC. It is stirred with cooling until one a dry and homogeneous powder with even kasta brown color achieved.

Mixture B

You proceed in the same way as in A, but pay attention to work at a temperature not 40 ° C exceeds. It brings the powder of the mixture A in the hopper of an extruder and the Pul ver of the mixture B in the feed hopper the ande ren extruder.  

The nozzle temperatures are 100 ° C for A or 90 ° C for B and the coextrusion die is brought to a temperature controlled by 90 ° C.

Upon exiting the nozzle, the resulting mixed Belt by running a bath of cold water cooled.

Subsequently, the belt to the desired lengths cut and a closure system (buckle) is on one of the ends clamped.

The dimensional criteria, determined by the shape of the nozzle are determined in the following:

- total width | 15 mm - width of the insecticidal part (maroon) 10 mm - width of the fatty acid part (yellow) 5 mm - thickness 3 mm

Example 9

Mixture A

Mixture B

It goes into the production and the extrusion as described in Example 8 before.

With the dimensions of the nozzle for coextrusion one obtains a white and black belt whose dimensions are in following are indicated:

- total width | 20 mm - width of the insecticidal part (white) 15 mm - width of the fatty acid part (black) 5 mm - total thickness 2.5 mm

Example 10

Mixture A

Mixture B

The mixed belt obtained after coextrusion has the following dimensions:

- total width | 15 mm - width of the insecticidal part (black) 10 mm - width of the fatty acid part (yellow) 5 mm - total thickness 3 mm

Clinical examinations

Different in a group of dogs and cats Age and different race were clinical sub carried out the various investigations Skin irritation by wearing an insecticidal neck bandes showed.

The incorporation of unsaturated essential fatty acid ren with C₁₈-C₂₂ in free or esterified form and ins particular of acids with C₁₈, which is the constituent of Vitamin F form, made possible in an insecticidal collar Light it, the phenomena on the skin to a minimum to reduce.

First comparison experiment

The trial consists in the treatment of two groups (P₁ and P₂) of dogs of different sex, Age and different race. Each group included 500 individual animals.  

The investigation was conducted during a period of 10 Weeks were performed, and the condition of the animals was all two weeks after the attachment of the collar under examined.

The skin irritation, which is considered during the examination was, was:

• - scales
• - Erythema
• - itching
• - Hair loss in the neck area

The examined collars showed the following tion (weight percent) on:

The collars of the type C₁ are on the animal group P₁ attached.

The collars of the type C₂ be the animal group P₂ attached.

Table I shows the results found where the numbers indicate the number of animals, the local ones Incompatibility signs showed.  

Table I

Second comparison test

An identical comparison experiment was conducted with two groups performed by cats P₁ and P₂, the collars C₁ and C₂ of the preceding example contributed.

The results are listed in Table II.

Table II

In experiments 1 and 2, the two compositions are gene of the collars C₁ and C₂ to 93% effective to combat of parasites (fleas and ticks) present on the animals.

The parasite-free animals become 100% during the 10 weeks of the investigation protected.

In this case, the local result incompatible phenomena alone by wearing the collar and not by excessive scratching or injury caused by the presence of fleas become.  

third try

You choose six dogs, who wore the collar C₂ (compare Experiment 1) as well as seven cats that have the neck Band C₂ contributed (see experiment 2).

All these animals show skin reactions. You take them the collar C₂ and sets them the collar C₁ to.

These animals are observed for five weeks. The Er results (see Table III) show that the invent The formulation according to the invention (which contains neutral vitamin F enriched) the disappearance of the skin reactions in short time allows.

Table III

Claims (16)

1. An antiparasitic collar for animals of at least one insecticidal substance, a macromolecular carrier and additives, characterized in that it

• (a) at least one free or esterified unsaturated fatty acid with C₁₈ to C₂₂ in association with the insecticidal substance as the active ingredient,
• (b) a thermoplastic solid macromolecular carrier, except polyurethane,
• (C) additives such as plasticizers and / or inert fillers and / or dyes and / or deodorants and / or stabilizers and / or diffusion regulators

that contains therein the proportion of the insecticidal substance between 5 and 25%, the proportion of unsaturated fatty acids between 1 and 10%, the proportion of the macromolecular carrier between 10 and 50% and the proportion of supplements between 1 and 15%, and that it is in the form of two laterally belt connected to form a mixed Doppelrie mens, wherein a belt is the insecticidal substance, the others containing the fatty acid and each of the two parts of the belt Carrier and for the insecticidal substance and for the chosen unsaturated essential fatty acid suitable additives ent holds. 2. collar according to claim 1, characterized marked records that the insecticidal substance is selected from the organochlorine compounds and / or organophos phosphorus compounds and / or carbamates and / or pyrethrum compounds and / or formamidines.   3. Collar according to claim 2, characterized that the organochlorine compounds are selected from the group of 2,2-dichlorovinyl-dimethyl phosphate, 1,2-dibromo-2,2-dichloroethyl methyl phosphate and 2-chloro- (2,4,5-trichlorophenyl) -vinyl dimethylphosphate. 4. Collar according to claim 2, characterized that the organophosphorus substance is selected from Group of O, O'-diethyl-O- (2-isopropyl-4-methyl 6-pyrimidinyl) thionophosphate and O, O-di ethyl-O- (2-isopropyl-4-methyl-6-pyrimidinyl) phosphate. 5. Collar according to claim 2, characterized that the carbamates are selected from 2,2-dimethyl 1,3-benzodioxol1-4-ol (N-methylcarbamate) and 2-isopropoxyphenyl (N-methylcarbamate) and 1-naphthyl-N-methylcarbamate. 6. Collar according to claim 2, characterized that the substances are selected from the pyrethrum type from α-cyano-3-phenoxybenzyl-2,2-dimethyl-3- (2,2-di chloro-vinyl) -cyclopropane carboxylate, α-cyano-3-phenoxybenzyl-2- (4-chlorophenyl) -3-methyl butyrate, 5-benzyl-3-furylmethyl-2,2-di methyl-3- (2-oxo-2,3,4,5-tetrahydro-3-thienylidenmethyl) - cyclopropane carboxylate, 3-phenoxybenzyl 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropancarboxy lat and (3,4,3,6-tetrahydrophthalimido methyl) -chrysanthemat. 7. Collar according to claim 2, characterized the formamidines are selected from N '- (4-chloro) O-tolyl) -N, N-dimethylformamidine and N-methyl-N'-2,4-xylyl-N- (N-2,4-xylylformamidoyl) - formamidine.   8. Collar according to one of claims 1 to 7, characterized characterized in that the essential unsaturated free or esterified fatty acids are selected from the group of oleic acid, linoleic acid, linolenic acid, Arachidonic acid, 11,14-eicosadienoic acid, docosahexane acid and its linear or branched C₁-C₄- Esters. 9. Collar according to one of claims 1 to 8, characterized characterized in that as fatty acids, the vitamin F used. 10. Collar according to one of claims 1 to 9, there characterized in that it is substantially gebil det is by association of O, O'-diethyl-O- (2-iso propyl-4-methyl-6-pyrimidinyl) -thionophosphat- Vitamin F. 11. Collar according to claim 1, characterized that the mixed belt by common hot Extrusion is obtained. 12. Collar according to claim 1, characterized that the mixed belt by molding or Formpres is obtained.   13. Collar according to one of claims 1 to 12, characterized characterized in that each of the two parts of mixed belt of different coloring substances and / or pigments and / or light-reflecting sub punching and / or luminescent substances. 14. A method of making an antiparasitic neck Tape according to one of claims 1 to 13, characterized characterized in that two different homogeneous Mixtures produced, with a 5 to 25% minde contains at least one insecticidal substance and that other contains 1 to 10% of at least one fatty acid, that the two mixtures separated into two Beschic kung funnel of an extruder with double System and that one at the time of Run through the common spray nozzle head performs lateral welding. 15. The method according to claim 14, characterized that the two mixtures in two different strand Pressing devices are extruded on the off occurs connected by a single extrusion head are.